chemical reactions electronic supplementary information

Electronic Supplementary Information (ESI) for

Bis(terpyridine) Ru(III) complexes functionalized porous polycarbazole for visible-light driven chemical reactions

Dejene Assefa Anito,a,b Tian-Xiong Wang,a,b Hai-Peng Liang,a Xuesong

Ding,*,a,b Bao-Hang Han*,a,b

a CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS

Center for Excellence in Nanoscience, National Center for Nanoscience

and Technology, Beijing 100190, China

b University of Chinese Academy of Science, Beijing 100049, China

Tel: +86 10 8254 5576. Email: [email protected]

Tel.: +86 10 8254 5708. E-mail: [email protected]

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Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2021

mailto:[email protected]

mailto:[email protected]

Materials and general characterizations

All the chemicals and solvents were purchased with high-purity level. Unless

otherwise stated, all reagents were used without further purification. 2-Acetylpyridine

(98%), 3,5-dibromobenzaldehyde (98%), carbazole (98%), copper iodide (CuI, 98%),

and iron(III) chloride (FeCl3, 98%) were purchased from Energy Chemical Ltd. 1,3-

Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU, 98%), anhydrous chloroform

(CHCl3, ≥99%), and methanol (CH3OH, 98%) were purchased from Sigma-Aldrich.

Ruthenium trichloride hexahydrate was purchased from bidepharm PLC.

Instrumentations and characterization

1H and 13C NMR spectra were recorded on a Bruker DMX400 NMR spectrometer.

Solid-state 13C cross-polarization magic angle spinning (CP/MAS) NMR data were

obtained from Bruker Advance III 400 spectrometer (Bruker, Germany). Mass spectrum

was measured with a Microex LRF MALDI-TOF mass spectrometer. The thermal

stability of the polymers was investigated in nitrogen atmosphere from room

temperature to 800 °C with increase of 10 °C min–1 (Diamond TG/DTA, Perkin Elmer).

The UV-vis absorption spectra were collected by Agilent Cary 5000 UV-vis-NIR

spectrometer. Fluorescence emission spectra were measured with FS5

spectrofluorometer (Edinburgh Instruments, United Kingdom). The infrared (IR)

spectra were obtained using a Perkin Elmer Spectrum One Fourier transform infrared

(FT-IR) spectrometer (Perkin Elmer, USA). Gas sorption isotherms were obtained with

Micromeritics TriStar II 3020 surface area and porosity analyzer (Micromeritics

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Instrument Corporation, U.S.A.). The samples were degassed overnight at 120 °C. The

obtained adsorption–desorption isotherms were evaluated to give the pore parameters,

including Brunauer–Emmett–Teller (BET) specific surface area, pore size, and pore

volume. The pore size distribution (PSD) was calculated from the adsorption branch

with the nonlocal density function theory (NLDFT) approach. X-ray photoelectron

spectroscopy (XPS) data were obtained from an ESCA-Lab220i-XL electron

spectrometer (VG Scientific Ltd., U.K.). The metal contents were measured by

inductively couple plasma-optical emission spectroscopy (ICP-OES 715 ES, Varian,

USA) after digesting the polymers completely in mixture of nitric acid and sulfuric acid

(V:V = 2:1).

Cyclic voltammetry (CV) was performed at 25 °C using a EG&G Princeton Applied

Research VMP3 electrochemical work station (Biologic VMP3, France) at a scan rate of

100 mV s–1. The solid samples of CPOPs (10 mg) were mixed with 10 wt%

polytetrafluoroethylene (PTFE) and 4 mL ethanol under ultrasonication to obtain a well-

dispersed suspension. To prepare the working electrode, the suspension was drop-casted

on a Pt plate electrode and the resulting electrode was dried at 50 °C for 30 min prior to

measurements. Pt wire, Ag/Ag+ (0.1 M AgNO3 in CH3CN) serve as counter electrode

and reference electrode, respectively, and ferrocenium-ferrocene (Fc+/Fc) as the internal

standard. Tetrabutylammonium hexafluorophosphate (Bu4NPF6) (0.1 M in CH3CN) was

used as the supporting electrolyte.

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Electron paramagnetic resonance (EPR) spectra were collected with an ELEXSYS-II

E500 CW-EPR spectrometer (Bruker, Germany). The mixtures of polymer, capturing

agent 2,2,6,6-tetramethylpiperidine (TEMPO), and N,N-diisopropylethylamine (iPr2EtN)

in air-saturated DMF were irradiated by 23 W white LED lamp for 3 min prior to EPR

measurements.

Synthesis of 4'-(3,5-dibromophenyl)-2,2':6',2''-terpyridine

Into a 500 mL round bottom flask, 2-acetylpyridine (4.84 g, 40 mmol) and a solution

of 3,5-dibromobenzaldehyde (5.27 g, 20 mmol) in ethanol (10.0 mL) were added. Then,

KOH pellets (3.08 g, 85%, 40 mmol) and aqueous solution of NH3 (60 mL, 29.3%)

were added to the solution. The reaction mixture was stirred at 34 °C for 24 h, and then

it was allowed to cool to 20 °C, and the off-white solid was collected by filtration and

washed with ice-cold ethanol (10 mL). Recrystallization from ethanol afforded a white

crystalline solid of 7.9 g with 85% yield. 1H NMR (400 MHz, CDCl3) δ (ppm) 8.76 (d,

J = 4.3 Hz, 2H), 8.70–8.65 (m, 4H), 7.97 (s, 2H), 7.91 (t, J = 7.7 Hz, 2H), 7.77 (s, 1 H),

7.41–7.37 (m, 2H).

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Synthesis of 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-phenylene)bis(9H-carbazole)

A 100 mL flask was charged with 9H-carbazole (2.43 g, 14.55 mmol), 4'-(3,5-

dibromophenyl)-2,2':6',2''-terpyridine (2.10 g,4.50 mmol), CuI (0.19 g, 0.97 mmol), 18-

crown-6 (0.09 g, 0.32 mmol), K2CO3 (4.02 g, 40.50 mmol), and 1,3-dimethyl-3,4,5,6-

tetrahydro-2(1H)-pyrimidinone (DMPU, 0.32 mL). The reaction mixture was stirred

magnetically at 200 °C under N2 protection for 2 days. After cooling to room

temperature, the reaction system was quenched by 2 N hydrochloric acid, and the

mixture was washed with aqueous ammonia (NH3 (aq)) and water. Then, the mixture

was extracted with CH2Cl2 and the solvent was evaporated. After TLC analysis, the

crude product was purified with flash column chromatography using petroleum ether

and dichloromethane (v/v = 4/1) as eluent. The desired fraction was collected and

rotavaped, and finally it was dried in vacuum oven at 60 °C for 12 h to give the off-

white powder of 0.856 g with 30% yield. 1H NMR (400 MHz, CDCl3) δ (ppm) 8.87 (s,

1H), 8.72 (d, J = 7.0 Hz, 4H), 8.25 (s, 2H), 8.21 (d, J = 7.7 Hz, 4H), 7.93 (d, J = 9.7 Hz,

3H), 7.63 (d, J = 8.2 Hz, 4H), 7.50 (t, J = 7.7 Hz, 4H), 7.43–7.32 (m, 7H). 13C NMR

(101 MHz, CDCl3) δ (ppm) 156.17, 155.47, 148.95, 148.65, 142.49, 140.65, 140.18,

137.33, 126.34, 125.89, 124.87, 124.18, 123.71, 121.55, 120.50, 120.50, 119.21,

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109.74. MS (MALDI-TOF) m/z: calculated for C45H29N5: 639.76, found: 640.2.

Synthesis of [(TPYCz)2Ru](PF6–)2

RuCl3·3H2O (130 mg, 0.5 mmol) and 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-

phenylene)bis(9H-carbazole) (366 mg, 0.99 mmol) were added to a mixture of

ethanol/water (v/v = 1/1, 10 mL) in a round-bottom flask. The solution was refluxed

overnight under an argon pressure, and then KOH (190 mg) was added in and the

obtained mixture was kept refluxing for 2 h. After cooling to room temperature, the

solvent was evaporated. To the crude product, NH4PF6 solution was added. The organic

phase was extracted by DCM and the aqueous phase was discarded, the process

repeated, finally washed with water alone. The solvent was evaporated and the residue

was taken up in a minimal amount of acetonitrile, then poured into H2O (350 mL) to

give a heavy precipitate, which was filtered and dried in vacuum to give black solid

(yield = 43.0%). 1H NMR (400 MHz, CD3CN) δ (ppm) 9.02 (s, 4H), 8.56 (s, 4H), 8.51

(d, J = 8.2 Hz, 4H), 8.20 (t, J = 6.5 Hz, 8H), 8.08 (s, 2H), 7.80 (t, J = 7.9 Hz, 4H), 7.68

(d, J = 8.2 Hz, 8H), 7.50 (t, J = 7.7 Hz, 8H), 7.34–7.30 (m, 8H), 7.23 (s, 4H), 7.11–7.07

(m, 4H). 13C NMR (101 MHz, CD3CN) δ (ppm) 158.57, 158.52, 156.20, 141.47,

141.10, 141.05, 138.71, 128.15, 126.99, 126.19, 124.11, 121.28, 121.19, 121.10,

121.02, 120.92, 120.85, and 110.60.

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Synthesis of CPOP-32

The synthesis of CPOP-32 was according to the literature with slight modification, a

100 mL round bottom flask was charged with the ferric chloride (477 mg, 2.94 mmol)

and degassed for 10 minutes, and then added 20 mL of anhydrous chloroform under

nitrogen protection. In a 100 mL flask, 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-

phenylene)bis(9H-carbazole) (TPYCz) (223 mg, 0.37 mmol) was dissolved in 30 mL

anhydrous chloroform, and then transferred dropwise via dropping funnel to the ferric

chloride suspension. The resulted mixture was stirred at room temperature for 24 hours

under nitrogen protection. Methanol (50 mL) was added to the reaction mixture, and

then the system was kept vigorously stirring for 2 hours. The solid was filtered and

washed with tetrahydrofuran and chloroform. The obtained polymer was further

purified by Soxhlet extraction with methanol for 24 hours. The purified solid was

transferred to methanolic HCl solution (6 M, 50 mL) and heated for 2 days under

stirring (the methanolic HCl solution was replaced by fresh one every 24 h). The

precipitate was filtered, and subsequently washed with aqueous ammonia solution (10

wt%), and methanol, respectively. The resulting solid was finally purified through

Soxhlet extraction by methanol, and dried in vacuum oven at 80 °C for 12 h to give

CPOP-32 with 94% yield.

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Synthesis of CPOP-32-Ru

Synthesis of CPOP-32-Ru was conducted according to modified procedure. In 50

mL round bottom flask, CPOP-32 (134 mg, 0.21 mmol) was added to the suspension of

RuCl3·3H2O (55 mg, 0.21 mmol) in methanol (10 mL) under nitrogen atmosphere. The

reaction mixture was kept refluxing at 90 °C for 1 day, and then the product was filtered

and further purified by Soxhlet extractor using chloroform for 24 hours. Finally, the

product was dried in vacuum oven at 80 °C for 12 h, and then a dark orange powder

CPOP-32-Ru (90%) was obtained.

Synthesis of CPOP-32-Ru'

The CPOP-32-Ru' was synthesized according to a modified procedure. [(9,9'-(5-

([2,2':6',2''-Terpyridin]-4'-yl)-1,3-phenylene)bis(9H-carbazole))2Ru](PF6–)2

(Ru(TPYCz)2(PF6–)2, 360 mg, 0.26 mmol) was dissolved in 45 mL of anhydrous

chloroform and then the resulted solution was transferred dropwise to a suspension of

ferric chloride (750 mg, 4.62 mmol) in 30 mL of anhydrous chloroform. The mixture

was stirred at room temperature for 1 day under nitrogen protection. Methanol (50 mL)

was added to the reaction mixture, and then the system was kept vigorously stirring for

2 hours. Then the solid was filtered and washed with tetrahydrofuran and chloroform.

The solid was further purified by Soxhlet extraction with methanol for 24 hours. The

purified product was transferred to methanolic HCl solution (6 M, 50 mL) and heated

for 2 days under stirring (the methanolic HCl solution was replaced by fresh one every

24 h). Then the precipitate was filtered, and subsequently washed with aqueous

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ammonia solution (10 wt%) and methanol, respectively. The resulting solid was finally

purified through Soxhlet extraction by methanol, and dried in vacuum oven at 80 °C for

12 h to give CPOP-32' with 96% yield.

The product was used to synthesize CPOP-32-Ru'. CPOP-32' (134 mg, 0.21 mmol),

RuCl3·3H2O (55 mg, 0.21 mmol), and methanol (10 mL) were used to give CPOP-32-

Ru' of 89 % yield as dark orange powder.

Fig. S1. TGA curves of CPOP-32 and CPOP-32-Ru.

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Fig. S2. XPS spectrum of Ru 3p3/2 of the Ru catalysts supported on CPOP-32-Ru.

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Fig. S3. XPS spectrum for Fe 3p of the chelated Fe on the CPOP-32-Ru.

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Fig. S4. Cyclic voltammograms of CPOP-32-Ru (a and b), and CPOP-32-Ru' (c and d)

in deaerated CH3CN with 0.1 M Bu4PF6 as supporting electrolyte with scan rate of 100

mV s–1.

Table S1. Redox potentials (V) of CPOP-32-Ru and CPOP-32-Ru'.

Photosensitizer E0–0 E1/2(M/M–) E1/2(M+/M) E1/2(M+/*M) E1/2(*M/M–)

CPOP-32-Ru

CPOP-32-Ru'

2.55 a

2.43 a

–1.20 b

–1.23 b

1.40 b

1.38 b

–1.15 c

–1.05 c

1.35 d

1.20 d

a E0–0 is estimated from the intersection of UV-vis absorption and emission spectra. b All

potentials are given in volts versus the saturated calomel electrode (SCE). c E1/2 (M+/*M)

= E1/2(M+/M) – E0–0. d E1/2(*M/M–) = E1/2(M/M–) + E0–0.

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Fig. S5. EPR spectra for samples of CPOP-32-Ru (4.0 mg L–1) (a), and CPOP-32-Ru'

(4.0 mg L–1) (b) in aerated DMF (100 µL) containing TEMPO (6.4 × 10–2 mM) and

iPr2EtN (5.74 × 10–2 mM) at dark and after 5 minutes irradiation with 23 W white LED

lamp at ordinary condition.

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Fig. S6. Recyclability of CPOP-32-Ru photocatalyst in the sulfide oxidation of

methyl(phenyl)sulfane to (methylsulfinyl)benzene. The catalyst was recycled from the

reaction mixture by centrifugation, washed with methanol and dichloromethane, dried,

and reused in a fresh reaction solution.

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Fig. S7. The FT-IR spectra of CPOP-32-Ru before and after photocatalytic reactions.

Fig. S8. Nitrogen sorption isotherm curve of CPOP-32-Ru at 77 K after photocatalytic

reaction.

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Table S2. Oxidative amine coupling using CPOP-32-Ru and CPOP-32-Ru'

photocatalyst.

Entry 1 2 3 4 5 6 7

CPOP-32-Ru + – + – + + +

CPOP-32-Ru' – + – – – – –

Visible-light + + – + + + +

O2 + + + + – + +

KI – – – – – + –

p-Benzoquinone – – – – – – +

Yield [%] 99 91 NSD NSD 8.2 6.0 14.1

Note: NSD means no significant detection.

Standard Reaction Condition: CPOP-32-Ru (or CPOP-32-Ru') (1.0 μmol),

phenylmethanamine (0.7 mmol), dry acetonitrile (MeCN, 1 mL), air, 23 W white LED

lamp and room temperature. Conversions were determined by 1H NMR.

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Table S3. Controlled experiment to determine the specific condition by hydroxylation

of (4-methoxyphenyl)boronic acid by CPOP-32-Ru and CPOP-32-Ru' photocatalyst.

Entry 1 2 3 4 5 6 7 8

CPOP-32-Ru + – – – + – + +

CPOP-32-Ru' – + – – – – – –

Visible-light + + – + – + + +

Air + + + + + + – +

iPr2 + + + – + + + –

Yield [%] 97 96 NSD NSD NSD trace 28 NSD


Standard Reaction Condition: 4-methoxyphenylboronic acid (0.5 mmol), CPOP-32-

Ru (or CPOP-32-Ru') (2.5 µmol), iPr2EtN (1.0 mmol), DMF (5 mL), air, 23 W white

LED lamp and room temperature. Conversions were determined by 1H NMR.

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Table S4. Selective photocatalytic oxidation of sulfides.

Entry 1a 2b 3 4 5 6

CPOP-32-Ru

CPOP-32-Ru'

+

–

+

–

–

+

–

–

+

–

+

–

Visible-light + + + + – +

Air + + + + + –

Conv. [%] 97 96 95 NSD Trace 35


Standard Reaction Condition: CPOP-32-Ru (or CPOP-32-Ru') (1.25 μmol),

methyl(phenyl)sulfane (0.5 mmol), dried MeOH (0.5 mL), air, 23 W white LED lamp

and room temperature. Conversions were determined by 1H NMR. a Originally prepared

photocatalyst. b After 4th Cycle.

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1H NMR of 4'-(3,5-dibromophenyl)-2,2':6',2''-terpyridine.

1H NMR of 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-phenylene)bis(9H-carbazole).

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13C NMR of 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-phenylene)bis(9H-carbazole).

MALDI-TOF- MS of 9,9'-(5-([2,2':6',2''-terpyridin]-4'-yl)-1,3-phenylene)bis(9H-

carbazole).

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General procedure

Photocatalytic oxidative amine coupling of benzylamine

To a dry 5 mL flask containing CPOP-32-Ru (1.0 µmol), the respective substrate

(0.27 mmol, 33.9 µL) in MeCN (1 mL) was added. The balloon filled with O2 was

attached to the condenser and the reaction mixture was stirred by irradiating with a

white LED lamp (23 W) at a distance of about 10 cm until the reaction completed. The

reaction progress was monitored by TLC and upon disappearance of the starting

material, the polymer material was separated by centrifugation. After rotary evaporating,

the 1H NMR measurement for the crude reaction mixture in CD3CN was used to

determine reaction conversions and selectivities. 1H NMR (400 MHz, CD3CN) δ (ppm)

8.34 (s, 1H), 7.73–7.52 (m, 2H), 7.46–7.24 (m, 8H), 4.66 (s, 2H).

Oxidative amine coupling of thiophen-2-ylmethanamine

The catalysis with CPOP-32-Ru was performed as abovementioned. The product is

characterized according the general procedure. The reaction mixtures used are CPOP-

32-Ru (1.0 µmol) and the substrate (0.27 mmol, 26.9 µL) in MeCN (1 mL). 1H NMR

(400 MHz, CD3CN) δ (ppm) 8.53 (s, 1H), 7.52 (dd, J = 17.2, 4.9 Hz, 1H), 7.44 (d, J =

3.5 Hz, 1H), 7.27 (d, J = 4.9 Hz, 2H), 6.98 (d, J = 3.5 Hz, 1H), 6.96 (d, J = 2.5 Hz, 2H),

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4.91 (s, 2H).

Oxidative amine coupling of (4-chlorophenyl)methanamine




(400 MHz, CD3CN) δ (ppm) 8.44 (s, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.4 Hz,

2H), 7.39–7.29 (m, 4H), 4.77 (s, 2H).

Oxidative amine coupling of (4-methoxyphenyl)methanamine




(400 MHz, CD3CN) δ (ppm) 8.38 (s, 1H), 7.72 (d, J = 8.6 Hz, 2H), 7.27 (dd, J = 8.3, 4.2

Hz, 2H), 6.99 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 4.68 (s, 2H), 3.85 (s, 3H),

3.79 (s, 3H).

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Oxidative amine coupling of (4-fluorophenyl)methanamine





2H), 7.20 (t, J = 8.8 Hz, 2H), 7.11 (dd, J = 9.5, 6.1 Hz, 2H), 4.76 (s, 2H).

Oxidative amine coupling of p-tolylmethanamine





2H), 7.23 (d, J = 7.8 Hz, 2H), 7.16 (d, J = 7.9 Hz, 2H), 4.73 (s, 2H).

Oxidative amine coupling of pyridin-4-ylmethanamine



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(400 MHz, CD3CN) δ (ppm) 8.46 (s, 1H), 7.77–7.65 (m, 2H), 7.59–7.51 (m, 2H), 7.43–

7.36 (m, 2H), 7.32 (t, J = 8.7 Hz, 2H), 4.85 (s, 1H).

Oxidative amine coupling of furan-2-ylmethanamine




(400 MHz, CD3CN) δ (ppm) 8.15 (s, 1H), 7.64 (s, 1H), 7.46 (d, J = 11.7 Hz, 1H), 7.26

(d, J = 8.0 Hz, 1H), 6.88 (d, J = 3.4 Hz, 1H), 6.57 (d, J = 1.8 Hz, 1H), 6.31 (d, J = 3.1

Hz, 1H), 4.70 (s, 2H).

General procedure for hydroxylation of 4-formylphenylboronic acid

The mixture of 4-formylphenylboronic acid (75 mg, 0.5 mmol), CPOP-32-Ru (2.5

μmol, based on monomer), iPr2EtN (140 μL, 1.0 mmol), and DMF (5.0 mL) was stirred

under irradiating about 10 cm apart from a white LED lamp (23 W) for 10 hours with

monitoring the reaction progress using thin layer chromatography, and the reaction was

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stopped following disappearance of the starting material. 1H NMR (400 MHz, CD3CN)

δ (ppm) 10.06 (s, 1H), 7.80 (d, J = 7.7 Hz, 2H), 6.99 (d, J = 7.8 Hz, 2H), 6.29 (s, 1H).

Hydroxylation of phenylboronic acid


characterized according the general procedure. The mixture of phenylboronic acid (61

mg, 0.5 mmol), CPOP-32-Ru (2.5 μmol, based on monomer), iPr2EtN (140 μL, 1.0

mmol), and DMF (5.0 mL) was stirred under irradiating about 10 cm apart from a white

LED lamp (23 W) for 12 hours. 1H NMR (400 MHz, CD3CN) δ (ppm) 7.80 (d, J = 7.2

Hz, 1H), 7.50–7.37 (m, 4H), 6.33 (s, 1H).

Hydroxylation of (4-methoxyphenyl)boronic acid


characterized according the general procedure. The mixture of (4-

methoxyphenyl)boronic acid (76 mg, 0.5 mmol), CPOP-32-Ru (2.5 μmol, based on

monomer), iPr2EtN (140 μL, 1.0 mmol), and DMF (5.0 mL) was stirred under

irradiating about 10 cm apart from a white LED lamp (23 W) for 8 hours. 1H NMR (400

MHz, CD3CN) δ (ppm) 7.74 (d, J = 7.6 Hz, 2H), 6.94 (d, J = 7.5 Hz, 2H), 6.08 (s, 1H),

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3.83 (s, 3H).

Hydroxylation of (4-(4-cyanophenyl)boronic acid


characterized according the general procedure. The mixture of (4-(4-

cyanophenyl)boronic acid (73.5 mg, 0.5 mmol), CPOP-32-Ru (2.5 μmol, based on

monomer), iPr2EtN (140 μL, 1.0 mmol), and DMF (5.0 mL) was stirred under

irradiating about 10 cm apart from a white LED lamp (23 W) for 12 hours. 1H NMR

(400 MHz, CD3CN) δ (ppm) 7.92 (d, J = 7.5 Hz, 2H), 7.73 (d, J = 7.4 Hz, 2H), 6.41 (s,

1H).

Hydroxylation of (4-(methoxycarbonyl)phenyl)boronic acid


characterized according the general procedure. The mixture of (4-

(methoxycarbonyl)phenyl)boronic acid (90 mg, 0.5 mmol), CPOP-32-Ru (2.5 μmol,

based on monomer), iPr2EtN (140 μL, 1.0 mmol), and DMF (5.0 mL) was stirred under

irradiating about 10 cm apart from a white LED lamp (23 W) for 10 hours. 1H NMR

(400 MHz, CD3CN) δ (ppm) 8.00 (d, J = 7.5 Hz, 2H), 7.90 (d, J = 7.5 Hz, 2H), 6.36 (s,

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1H), 3.90 (s, 3H).

Hydroxylation of p-tolylboronic acid


characterized according the general procedure. The mixture of p-tolylboronic acid (68

mg, 0.5 mmol), CPOP-32-Ru (2.5 μmol, based on monomer), iPr2EtN (140 μL, 1.0

mmol) and DMF (5.0 mL) was stirred under irradiating about 10 cm apart from a white

LED lamp (23 W) for 8 hours. 1H NMR (400 MHz, CD3CN) δ (ppm) 7.69 (d, J = 7.4

Hz, 2H), 7.22 (d, J = 7.4 Hz, 2H), 6.19 (s, 1H), 2.92 (s, 3H).

General procedure for selective photocatalytic oxidation of sulfides

Oven dried 5 mL round bottom flask was charged with 0.5 mL dried MeOH, 0.5

mmol sulfides and CPOP-32-Ru (1.25 μmol, based on monomer), and the flask was

fitted with condenser. Under open air, the mixture was magnetically stirred with

irradiation of 23 W white LED lamp at a distance of around 10 cm. The reaction

progress was monitored using TLC. Once the reaction was completed, the photocatalyst

was collected by centrifugation and followed by evacuation of the solvent under

vacuum. The conversions and selectivities were determined by 1H NMR on the basis of

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the ratio between integrated peaks of product in CDCl3 as solvent. The crude product of

oxidation of thioanisole was taken as an example to illustrate the calculation procedure.

1H NMR (400 MHz, CDCl3) δ (ppm) 7.54–7.37 (m, 5H) and 2.64 (s, 3H).

Selective sulfide oxidation of (4-methoxyphenyl)(methyl)sulfane


characterized according the general procedure. The reaction mixtures used are substrate

(0.5 mmol, 70.0 µL), and CPOP-32-Ru (1.25 μmol, based on monomer) in 0.5 mL

dried MeOH. 1H NMR (400 MHz, CDCl3) δ (ppm) 7.30 (d, J = 8.6 Hz, 2H), 6.88 (d, J =

8.6 Hz, 2H), 2.47 (s, 3H).

Selective sulfide oxidation of (4-fluorophenyl)(methyl)sulfane




dried MeOH. 1H NMR (400 MHz, CDCl3) δ (ppm) 7.28 (dd, J = 8.1, 5.1 Hz, 4H), 2.49

(s, 3H).

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Selective sulfide oxidation of (4-chlorophenyl)(methyl)sulfane




dried MeOH. 1H NMR (400 MHz, CDCl3) δ (ppm) 7.23 (d, J = 1.9 Hz, 2H), 7.14 (d, J =

8.6 Hz, 2H), 2.43 (s, 3H).

Selective sulfide oxidation of methyl(p-tolyl)sulfane




dried MeOH. 1H NMR (400 MHz, CDCl3) δ (ppm) 7.21–7.13 (m, 2H), 7.08 (d, J = 7.7

Hz, 2H), 2.43 (s, 3H), 2.29 (s, 3H).

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